Diesel lubricating oil



United States Patent 3,206,399 DIESEL LUBRICATING OIL Robert H. Davis, Woodbury, and Richard G. Ramge, Sewell, N.J., assignors to Socony Mobil Oil Company, Inc., a corporation of New York No Drawing. Filed Sept. 29,1961, Ser. No. 141,580 3 Claims. (Cl. 252-405) The invention relates to lubricating oil compositions for use in diesel engines. More particularly, it is concerned with lubricating oils suitable for use in large, low-speed marine diesel engines.

In a copending application of Robert H. Davis, Serial No. 120,938, filed June 30, 1961, there is disclosed and claimed calcium acetate oil dispersions containing certain N-acyl-substituted sarcosines as stabilizing agents. As pointed out in the copending application, these singlephase stabilized calciumacetate oil dispersions are highly desirable for use as marine diesel lubricants, offering the advantage over emulsion-type lubricating oils of superior storage stability. Also, due to their high acidneutralizing power, the calcium acetate dispersions greatly minimize corrosion problems normally associated with the operation of diesel engines. They also exhibit advantageous extreme pressure and anti-wear properties.

Although the stabilized single-phase calcium acetate oil dispersions thus provide many highly desirable properties for use as marine diesel oils, experience in such use Thus, in the has indicated certain deficienciestherein. operation of trunk-type diesels, wherein the oil is continuously recycled to the cylinders, it' is essential that the oil exhibit the highest possible resistance to oxidation.

provided by the incorporation in the N-acyl-sarcosine stabilizedcalcium acetate dispersion of a minor proportion of an oil-soluble carbonated sulfurized basic calcium alkyl phenate.

It has been found, furthermore, that the use of the carbonated, sulfurized basic calcium alkyl phenate additive in combination with the stabilized. calcium acetate dispersion provides marine diesel oils which form friable port deposits of'the type which breakaway during operation of the engine and do not contribute to exhaust port" closure. The low port-cloggingtendency of the oil thus provided by the invention is surprising in that the use ofphenolic-type additives in marine diesel oils, though advantageous in other respects, ordinarily has the drawback that they contribute to the formation of hard, tenacious port deposits of the type which cause exhaust port clog-- ging. The use of the carbonated, sulfurized basic calciumalkyl phenate in the calcium acetate dispersion oils, however, does not result in this type of:deposit. present invention, therefore, provides a marine diesel oil composition having high' oxidation stability and waterresistivity, as well as low port-clogging tendencies.

It has also been found Theice

Accordingly, it is a prime object of this invention to provide a new and highly advantageous marine diesel oil composition comprising an N-acyl-substituted sarcosinestabilized calcium acetate dispersion having incorporated.

therein a minor amount of a carbonated, sulfurized basic calcium alkyl phenate. Other and further objects of the invention will be apparent from the following description thereof.

As pointed out in the aforesaid copending application, the N-acyl-substituted sarcosines which are utilized as stabilizers for the calcium acetate oil dispersions in accordance with the invention conform to the formula:

0 ll R-C-N-CHzCOOH wherein R represents an aliphatic hydrocarbon radical having from about 8 to about 24 carbon atoms and which may be either saturated or unsaturated. Typical examples of these sarcosines are the following:

N-pelargonoyl sarcosine N-undecyloyl sarcosine N-lauroyl sarcosine N-myristoyl sarcosine N-palmitoyl sarcosine N-stearoyl sarcosine N-oleoyl sarcosine N-linoleoyl sarcosine N-arachidoyl sarcosine N-behenoyl sarcosine N-heyenoyl sarcosine A number of the N-acyl-substituted sarcosines are available commercially under the trade name Sarkosyl, for example, Sarkosyl L (lauroyl sarcosine), Sarkosyl O (oleoyl sarcosine) and Sarkosyl S (stearoyl sarcosine).

As further pointed out in the copending application, either anhydrous or hydrated calcium acetate may be used in forming the calcium acetate oil dispersions. The calcium acetate may either be preformed or it may be formed in situ. When using preformed calcium acetate, the dispersion is prepared by forming a mixture of the calcium acetate, the N-acyl-sarcosine and the base oil and stirring the mixture for a short period, say, from a few seconds up to about 30 minutes atv a temperature of from about 25 C. to about 200 C. and preferably from about 50 C. to about 150 C. Although stable dispersions can be formed at room temperature with only a brief initial mixing of the calcium acetate,,the sarcosine compound and the oil andv allowing the mixture to stand for several hours, its formation is considerably hastened by heating and stirring the mixture. Also, if desired, the mixture may be subjected to a mechanical homogenization treatment although this step is not essential.

The calcium acetate. may be prepared in situ by neutralizing calcium oxide or calcium hydroxide with either acetic anhydride. or acetic acid in the. presence ofv the oil and then heating the mixtureto a temperature suflicient to remove anyfree water therefrom, i.e., above C. The N-acyl-sarcosine is then added and the. dispersion formed as in the case of the preformed calcium acetate;

The oil compositions of the present invention are prepared simply by blending. the carbonated, sulfurized basic calcium alkyl phenate additive with the calcium acetate dispersion and, if necessary, then diluting the .blend with additional base oil to obtain the desired final oil viscosity.

The sulfurized basic calcium alkyl phenates, which after carbonation are utilized in the present invention,

are fully described in US. Patent No. 2,680,096. The carbonated version of these additives is fully disclosed in a copending application of Ferdinand P. Otto, Serial No. 782,660, filed December 24, 1958, now US. Patent No. 3,036,971, issued May 29, 1962.

As shown in Patent No. 2,680,096, the basic sulfurized calcium phenates contain a ratio of equivalents of calcium to equivalents of phenol which is substantially greater than that of the corresponding normal sulfurized calcium phenates. Thus, they contain up to about two full equivalents of calcium per equivalent of phenol as compared to the corresponding normal salts which contain only one equivalent of calcium per equivalent of phenol.

On a. percentage basis, therefore, the basic sulfurized by dissolving the basic salt in a suitable diluent, such as j mineral oil, heating the solution to a temperature of from about 200 F. to about 400 F. and passing carbon dioxide through the heated solution for a time sufficient I to incorporate from about 0.2 mol to about 0.6 mol of carbon dioxide per mol of calcuim into the basic salt. The following example illustrates the preparation of a typical carbonated, sulfurized basic calcium alkyl phenate .salt viz., the carbonated, sulfurized basic calcium alkyl j phenate of propylene tetramer-substituted phenol.

EXAMPLE 1 (1a) Preparation of propylene tetramer alkylated phenol A mixture consisting of 300 parts, by weight, of phenol,

f 555 parts, by weight, of a polypropylene comprised essentially of propylene tetramer (average M.W.==170) and 45 parts, by weight, of acid-treated clay were heated at 300 F. for a period of 12 hours after which time the mixture was filtered. The filtered mixture was then heated to 530 F. to remove unreacted phenol and olefin polymers. The resulting propylene tetramer-alkylated phenol product hada boiling range of 560 F. to 700 F.

i (b) Preparation of sulfurized basic calcium phenate of propylene tetramer-alkylated phenol A mixture of 600 parts, by weight, of the alkylated phenol product of (a), above, 173 parts, by weight, of

, calcium hydroxide, 58 parts, by weight, of sulfur and 300 parts, by weight, of ethylene glycol was heated at 300 F. with agitation at an absolute pressure of 300 3 millimeters of mercury. After the water of reaction had been distilled off, the pressure was reduced to 60 millimeters of mercury and the temperature raised to 380 F.,

at which temperature and pressure the ethylene glycol was removed. i glycol was being removed, 1000 parts, by weight, of I petroleum lubricating oil were added. When all of the During the period when the ethylene ethylene glycol had been removed, the mixture was cooled and 200 parts, by weight, of a petroleum thinner were addedand the mixture filtered. The filtrate was heated at reduced pressure to remove the petroleum thinner. The final lubricating oil solution (containing about 40% of the basic calcium salt product) analyzed 2.9%

f sulfur and 4.4% calcium; the basic sulfurized calcium 7 alkyl phenate containing about 70% more calcium than that present in the corresponding normal alkyl phenate.

(c) Preparation of carbonated, sulfurized basic calcium phenate of propylene tetramer-alkylated phenol Thirty gallons of a product prepared as in (b) and having sulfur and calcium contents similar thereto was constantly agitated with an anchor type stirrer, while carbon dioxide was introduced into the liquid through a A" copper tube at a rate of 10 pounds per hour. The treatment was continued for four hours.

Samples taken hourly showed no evidence of deposits or change in clarity. CO contents were as follows:

Percent CO Hours combined in additive O 0.1 1 1.4 2 1.6 3 1.7 4 1.9

Analysis of 4-hour product:

Percent Ca s.. 4.4 Percent C0 1.9 KLV. at 210 F., cs. 25.05 Percent S- 2.8

The preparation of a marine diesel oil composition typical of the invention is shown in the following example:

EXAMPLE 2 (a) Preparation of stabilized calcium acetate-oil dispersion Amount (parts Materials used: by weight) Calcium acetate (containing 6% water, i.e., ap-

proximately mol water of hydration) 40 Oleoyl sarcosine 3 Base oil (Solvent-refined coastal, SUV:500

Procedure.The oleoyl sarcosine was added to a slurry of the calcium acetate in the base oil and the mixture stirred and heated over a period of /2 hour to a final temperature of about 135 C. The mixture was then cooled to about C. and passed through a Manton- Gaulin homogenizer-operating at 3000 p.s.i. The resulting dispersion had excellent fluidity and exhibited only a slight haze.

(b) Preparation of marine diesel oil composition To 80 parts: (by weight) of base oil (a mixture of 72 parts of solvent-refined coastal stock, SUV:500 F. and 8 parts of solvent-refined coastal bright stock, SUV:3300 100 F.), there was added with stirring 10 parts of the calcium acetate dispersion prepared in (a) and 10 parts, by weight, of the carbonated, sulturized basic calcium alkyl phenate of propylene tetrarner-alkylated phenol (Example 1). Theresulting oil was an op tically clear SAE 50-grade oil having a TBN (total base number) of 40 as determined by ASTM Method D-664.

The marked improvement in the high temperature oxidation stability and water resistance of the calcium acetate dispersion affected by the incorporation of the car bonated, sulfurized basic calciumalkyl phenate and the unexpectedly low port+clogging tendencies of theoil compositions of the invention have been demonstrated by the following tests.

Oxidation stability test.--This test determines the stability of an oil under high temperature catalytic oxidation conditions. This test is conducted as follows: A 25 cc. sample of the oil is placed in a 200 x 25 mm. test tube with 15.6 square inches of sand-blasted iron wire, 0.78 square inch of polished copper wire, 0.87 square inch of polished aluminum wire and 0.167 square inch of polished lead surface. The oil is heated to 325 F. and dry air is passed-through it at a rate of 10 liters per hour fora period of 40 hours. The viscosity of the oil is determined before and after the test as a measure of the extent to which the oil is oxidized during the test. Thus, the greater the increase in the viscosity of the oil the greater the deterioration of the oil. The results of this test are given in Table I. Percent Oil Tested 'TBN Port Nature of TA BDE -'I.-OXIDA[DION .DEST 5 Clogging Deposit KV@ KV@ Iferce it Oil containing carbonated, sulfurized 40 55 Hard and Oil Composition Tested 210 F. 210 F. Viscosity basic calcium phenate of propylene tenacious. Initial Final Increase tetramer-alkylated phenol [Example 1(0)] only. Example No. 2(b); 40 30 Soft and Example 2(a) 19.28 58. 95 206 d Example 2 0 18.32 20 a p I Itwill be observed-from Table II that the amount of It IS Seen these.r.esults that F 3 t port clogging obtained by the use of thecalciumacetate tion of the 011 9 9 the .mventlon pt phenate combination isalrnost /2 less than that with the g f g g sulfutlzed basllc m 1 i g phenate alone and-that the type ofdeposit in the one is xglnp e was extrenwy W 1 e at o e of the soft type not conducive to port closure, while that Stablhzed calclum acetate dlsperslon alone [Example of the latter is of the hard type which induces port closure. 2(a)] was Substantlal' Although the oil composition of the invention shown in Check valve test.-This test indicates the ability of a Example 2(1)) on the basis of the active ingredients dlgsel 011 hi has i g Wlth water contained 4% of calcium acetate, 0.3% of oleoyl sarcosine .reslst p p under t e temPerailre conand 4% of the carbonated, sulfurized basic calcium alkyl dmons lmstmg 5 check Yalves and lines mnmng along phenate additive, it will be appreciated that the amounts the engm.e.extenor and mm F of the respective additives can be varied considerably decompos 1tlon products an mfenor. .lubncant W111 Within the scope of the invention, the specific amounts Vent lubrtcant f Wh1.1e decomposltlon priducts i a used depending upon the particular operating conditions good lubncant W111 i putnpable and provide t' encountered, such as the sulfur content of the fuel betion along with the oil. In this test 5 parts of the test 011 ing used cm In general therefore the amount of and 95 parts of water are shaken together and the m xture cium acetate additive employed may suitably range from allowed to settle. The heavy severely water-contaminated about 0.5% to about 20%, while the amount of the portion which settles out is separated and Sub ected to a Sarcosine compound may vary from about 0.05% to check Valve pumpmg test follows A Manzen.lubn' about 5%, the preferred amounts being from about 2% Gator and check Valve (opempg presinlre 50 6O Z are to about 8% and from about 0.1% to 2.0%, respectively. used valve and asoclated. Inpmg are g i i correspondingly, the concentration of the carbonated, at 300 m an 9 Wlnle the 011 pumpedt p t e sulfurized basic calcium alkyl phenate additive may range valve. The test is continued for 14 days or until either from about 0.5% to about 20%, the preferred amount (1) the 011 becomes unpumpable or (2) deposlts i h being from about 2% to about 8%. It will be undervalve.prevent flow of on therethrqugh'. O11 W111 stood that the amounts of the several additives recited funcuon throughoulf the test An mfenor O11 W111 Q herein, including the following claims, in all cases reprem6 wmparttlve Fests conducted on the stablhzefi sent weight percentages of the active ingredients, i.e., the calcium acetate dispersion of Example 2(a) and the o l 40 additive compounds per composition of the Present lflventlon It The oil compositions of this invention may also conwas found that the forms a grease It tain other additives designed to provide various improvcomes urfpumpablei falls f test m aPPr9Xmate1Y 4 ing efiects therein, such as antioxidants, detergents, visdays, while the latter oil functions for the entire duration cosity improve, pour point depressants, antimlst agents of the test. Accordingly, it is seen that the oil composi- 4 defoamants, em tion of the invention, utilizing the carbonated, sulfurized a Althbugh the present invention has been described in basic calcium alkyl Phenat? combmatlon Wlth E q terms of specific embodiments and examples thereof, it persed calcium acetate, exhibits excellent water-resistivity, is not intended that the scope of the invention be limited whereas the calcium acetate dispersion 011, without the in any way thereby except as indicated in the following carbonated, sulfurized basic calcium alkyl phenate, is inclaims ferior in this respect. What is claimed Marine port-clogging teSt. mfiasures the P Q 1. A single-phase lubricating oil composition having Clogging a manna dlesel PE A Homehte improved high temperature oxidation properties compris- Y e englne 1S Operate}1 under Conditions to Pl ing a major proportion of a mineral lubricating oil, from P deposits in a Short tlme- The apparatus corfslsts of about 0.5% to about 20% of calcium acetate, from about foul Parts! a motomd Home/lite y 61181116, 0.05% to about 5% of an N-acyl-substituted sarcosine an external lubrication system to meter the test lubricant compound f the form l through three points around the Homelite cylinder, (3) O a fuel burner to produce combustion gases and (4) a duct l NC system to guide the exhaust gases from the burner through R b Hzooofl the exhaust ports of the Homelite engine. The engine CH3 operating conditions are as follows: where R represents an aliphatic hydrocarbon radical of from about 8 to about 24 carbon atoms and from about Speed r.p.m 36 0.5% to about 20% of a carbonated, sulfurized basic Fuel consumption lbS./hr 1. 5 5 calcium alkyl phenate having from about 4 to about 30 Air/ fuel ratio 1 1 carbon atoms per alkyl group therein. Preheated temperature F 200 2. A single-phase lubricating oil composition having Exhaust temperature F 700-800 improved high temperature oxidation properties compris- Smoke level (Bacharach smoke scale) 10 9+ ing a major proportion of a mineral lubricating oil, from Oil feed rate gms./hr 27 about 0.5% to about 20% of calcium acetate, from about Duration of test h0urs 6 0.05% to about 5% of oleoyl sarcosine and from about 0.5% to about 20% of a carbonated, sulfurized basic The amount and yp of exhaust P dePOSItS formed calcium alkyl phenate of propylene tetramer-alkylated are rated visually at the end of the test. The test results h L are presented in Table II. 3. A single-phase lubricating oil composition having improved high temperature oxidation properties compris- 2,944,023 7/60 Kolarik 25249.5 X ing a major proportion of a mineral lubricating oil, 3,019,187 1/62 Panzer et al 25240.7 from about 2% to about 8% of calcium acetate, from 3,036,971 5/62 Otto 252-42.7

about 0.1% to about 2% of oleoyl sarcosine and from about 2% to about 8% of a carbonated, sulfurized basic 5 calcium alkyl phenate of propylene tetramer-alkylated 844,426

phenol.

FOREIGN PATENTS 8/60 Great Britain.

OTHER REFERENCES Geigy Surfactants, Geigy Industrial Chemicals, copyright 1959; page 2 relied on.

' Zussman et al.: Acylated Amino Acids in Shampoos.

References Cited by the Examiner UNITED STATES PATENTS 10 4/57 Spivack et a1 252-5 1.5 in Journal of the Society of Cosmetic Chemists. vnl A 12/59 Bradley et a1. 252--42.7 No. 5, December 1955; pages 407-415.

3/60 Morway 252--39 3 /6() Morway 252 4 5 DANIEL E. WYMAN,- Primary Examiner.

6/60 Morway 15 JOSEPH R. LIBERMAN. Examiner, 

1. A SINGLE-PHASE LUBRICATING OIL COMPOSITION HAVING IMPROVED HIGH TEMPERATURE OXIDATION PROPERTIES COMPRISING A MAJOR PROPORTION OF A MINERAL LUBRICATING OIL, FROM ABOUT 0.5% TO ABOUT 20% OF CALCIUM ACETATE, FROM ABOUT 0.05% TO ABOUT 5% OF AN N-ACYL-SUBSTITUTED SARCOSINE COMPOUND OF THE FORMULA 